Salicyloylamino-anthraquinone pigments

ABSTRACT

PIGMENT OF THE FORMULA   1-(X-NH-),2-Y2,3-Y3,4-Y4,5-Y5,6-Y6,7-Y7,8-Y8-ANTHRAQUINONE   ARE OF YELLOW COLOR WTH A GREENISH HUE. THEY ARE DISTINGUISHED BY PARTICULARLY GOOD WEATHER AND LIGHT-FASTNESS AND FASTNESS TO SOLVENTS.

United States Patent O 3,799,952 SALICYLOYLAMINO-ANTHRAQUINONE PIGMENTS Andre Pugin, Rieh'eu, and Kurt Burdeslra and Ernst Model, Basel, Switzerland, assiguors to Ciba-Geigy AG, Basel, Switzerland No Drawing. Original application Sept. 21, 1969, Ser. N

854,770, now Patent No. 3,682,966. Divided and this application July 13, 1971, Ser. No. 162,254 Claims priority, application Switzerland, Sept. 13, 1968, 13,770/68 Int. Cl. C09b 1/42, N54 US. Cl. 260-377 ABSTRACT OF THE DISCLOSURE Pigments of the formula Y1 Ya Ya Y are of yellow color with a greenish hue. They are distinguished by particularly good weather and light-fastness and fastness to solvents.

This application is a division of application Ser. No. 854,770, filed Sept. 2, 1969, now US. Pat. 3,682,966.

DESCRIPTION OF THE INVENTION The present invention concerns new antbraquinone pigments, processes for the production thereof and their application for the pigmenting of high molecular organic material.

It is known that l-salicyclic acid amidoanthraquinones are suitable as pigments. Pigments of this series are thus known wherein the salicyclic acid radical is substituted'by chlorine. These pigments usually have a very good fastness to light but the other fastness properties, especially fastness to migration and cross-lacquering, are not good, so that their use'in lacquers and plastics is extremely limited.

It was therefore not foreseeable that the antbraquinone pigments, according to the invention, would have the desired properties, at the same time preserving their good fastness to light. The compounds concerned are of the Formula I,

I /RI] wherein n represents or 2 6 Claims 3,799,952 Patented Mar. 26, 1974 R represents hydrogen and R represents the acyl radical of the formula HI,

wherein R represents an alkyl radical having 1-4 carbon atoms, a monoor binuclear aryl radical, a heterocyclic or hydroaromatic radical, or the radical OR or NHR wherein R denotes an aromatic or an aliphatic radical having 14 carbon atoms, or R and R represent, together with the nitrogen atom, an optionally condensed, 5- or 6- membered, cyclic dicarbimide radical, and the phenyl radical A can be substituted by halogen, trifluoromethyl, methoxy or alkyl having 14 carbon atoms. 7

In the compounds of the Formula I, one or several of the symbols Y to Y can for example represent chlorine or bromine, whereby in particular the 4-chloro, S-chloro, 6,7'dichloro, 5,6,7,8-tetrachloro and the 2,4-dibromo-substituted anthraquinone compounds are preferred.

The Y-substituents can also represent the methyl or methoxy radical, whereby the Z-methyl, 4-methoxy, 4- methoxy-S-chloro or the Z-methyl-4-chloroanthraquinone compounds are particularly important. One of the substituents Y Y and Y can also denote the -NH -group, whereby the NH -group, in its turn, can be substituted by the acyl radical of an optionally substituted benzoic acid, amongst others also by the radical X. Thus in Formula I, the antbraquinone radical can contain for example in 4-position, the benzoylamino group.

In Formula II, the phenyl nucleus A can be substituted, e.g. by chlorine, bromine, the methyl or methoxy group. The acid amide group or the ring-closed acid imide group can be present singly or twofold.

In the acyl radical of the Formula III of the acid amide group, R represents a lower alkyl radical having 1-4 carbon atoms, a monoor binuclear aryl radical, e.g. the phenyl radical, a phenyl radical substituted by halogen, alkyl, alkoxy or acylamino groups, the diphenyl or the naphthyl radical; furthermore, R can represent a heterocyclic radical such as, e.g. acid derivatives of pyridine, or a, hydroaromatic radical. In the acyl radical of the Formula III, R can also represent, e.g. the radical OR., or -NHR The acyl group can also be, therefore, an aromatic or an aliphatic urethane or urea group having preferably 1-4 carbon atoms.

Suitable acylated aminosalicyclic acid radicals of the Formula II, according to the invention, are for example the following:

-oc NHCOCH| -oc Nrrooocm.

-oc NH-C o- OCH; 7

HO I -O C I NH-C O- --OC NH-CO In Formula II of the salicylic acid ester, the acid .amide group can also be ring-closed, i.e. R and R can together form an optionally 5- or -6-membered cyclic carbimide radical, whereby the cyclic carbimide radical can be, e.g. an optionally substituted phthalimido group or-a pyridine dicarboxylic acid amide group.

The anthraquinone pigments, according to the invention, have an outstanding fastness to migration, solvents and cross-lacquering, in addition to an excellent fastness to weather and light. In general, they possess a good texture and can often be used in the form of their crude product. If necessary or desirable, the crude products can be converted, by grinding or kneading, into a finely dispersed form. Grinding auxiliary agents are thereby advantageously used, such as inorganic and/or organic salts in the presence or absence of organic solvents. An improvement in the properties can also frequently be achieved by heating the crudepigments in hot organic solvents. After ginding, the auxiliary'agents are removed in the usual manner, soluble inorganic salts being removed, for example, with water and water-insoluble organic auxiliaries, e.g. by steam distillation. Reprecipitaa deeply-colored, finely dispersed, transparent pigment fibre. Particularly preferred compounds falling under Formula I are those in which X represents (Hanna Hal represents chlorine or bromine, m represents from 0 to 4, a first of Y Y and Y represents the same as XNH, benzoylamino, chloro-benzoylamino, or hydrogen, and the second and the third thereof represent hydrogen; each of Y Y Y and Y, is hydrogen or chlorine.

Most preferred are those pigments falling under Formula I, wherein X represents N/ (Hal)...

TH! Ill) NH: (W) V Y:

whereinY to Y have the meaning given in Formula I, by reaction with a compound yielding the salicylic acid radical of the Formula II. Suitable as a compound yieldalso proceed by way of the radical of the Formula H with.

thel-aminoanthraquinone, corresponding to a reamidation reaction.

Moreover, the acylation can be performed with an aliphatic, aromatic, hydroaromatic or heterocyclic: (ortho) dicarboxylic acid, a dicarboxylic acid anhydride or -halide to the carbimide compound.

Suitable for the amide formation, according to the invention, are for example the following l-aminoanthraquinones l-aminoanthraquinone I 1-amino-4-chloroanthraquinone l-amino-S-chloroanthraquinone 1-amino 6,7-dichloroanthraquinone 1-amino 5,6,7, 8-tetrachloroanthraquinone 1-amino-2-methylanthraquinone 1 amino-6,7-dimethylanthraquinone 1-amino-2,4-dibromoanthraquinone 1-an1ino-4,S-dimethoxyanthraquinone l-amino-S,8-dimethoxyanthraquinone 1-amino-4-methoxyanthraquinone 1-amino-4-methoxy-5 -chloroanthraquinone 1-amino-2-methyl-4-chloroanthraquinone l-amino-4-benzoylaminoanthraquinone In the above given l-aminoanthraquinones, a second amino radical can be in 4-, 5- or 8-position and can be amino Substituent can optionally be present. This secondreacted, for example, with a further salicylic acid radical of the Formula II, or with an unsubstituted or substituted benzoic acid. According to the invention, the acylation of the l-aminoanthraquinone in the l-amino position is always etfected by a salicylic acid derivative yielding the salicylic acid radical of the Formula II.

The production of the pigments of the Formula I, according to the invention, can for example also be achieved by performing the acylation of the aminoanthraquinones with salicylic acids or -chlorides containing nitro groups, and then further acylating the obtained compounds, following the reduction of the nitro group(s) to the amino group(s) after the first acylation, in accordance with the explanations given above for the pigments of Formula I.

The new pigments of the anthraquinone series are suitable for the pigmenting of polymeric organic material, e.g. in printing inks for the printing industry, in paints having an oily base such as linseed-oil paints, or with an aqueous base such as dispersion paints, or in lacquers of varying kinds such as in nitrolacquers or stoving lacquers, having in the latter case, e.g. an alkyd resin or acryl resin base. They can also be used for the spinningdyeing of viscose or cellulose acetate, for the pigmenting of plastics such as polyethylene, polystyrene, polyvinyl chloride, whereby the latter can also contain softeners, also for the pigmenting of cellulose esters, curable resins or for the pigmenting of rubber. They are also applicable for the dyeing of paper pulp or for the coating of webs, e.g. in the production of laminated paper.

The following examples illustrate the invention without limiting it in any way. All temperatures are given in degrees centigrade.

EXAMPLE 1 O 01 H ii I 01 o NH-CO N 22.3 g. of l aminoanthraquinone and 46.3 g. of 2- hydroxy-S-tetrachlorophthalimido 1 benzoic acid are heated with 500 ml. of nitrobenzene to 105-110. Into the yellow suspension are then added, while stirring well and within 1% hours, 13.56 g. of thionyl chloride, dissolved in 50 ml. of nitrobenzene. When the formation of hydrochloric acid has subsided after about 30 minutes, the suspension is heated for 2 hours to 140-145" and, to complete the reaction, for a further 20 minutes to 160 165. After cooling to 110, the precipitated yellow product is filtered off, washed with nitrobenzene and then with alcohol, and dried at 110 in vacuo. By this means are obtained 61.5 g. of a greenish-yellow pigment of the above stated formula, which has a very good fastness to cross-lacquering, migration, light and weather.

If the Z-hydroxy 5 tetrachlorophthalimido-1-benzoic acid is replaced by equimolecular amounts of Z-hydroxy- 5-(4'-chloroor 4'-nitrophthalimido)-1-benzoic acid, 2- hydroxy-S-phthalimido-lbenzoic acid, 2-hydroxy-4-tetrachlorophthalimido-l-benzoic acid, or 2-hydroxy-4-phthalimido-l-benzoic acid, with the procedure being otherwise the same, then pigments are obtained having similar fastness properties to those stated above.

Furthermore, if the 22.3 g. of l-aminoanthraquinone are replaced by equimolecular amounts of one of the aminoanthraquinones listed in the following Table I, using otherwise the same procedure, then pigments are obtained having similar fastness properties and with the shades given in column 3 of the table.

TABLE I i Shade in paper Ex. Aminoanthraqulnone printing 2. laminoA-chloroanthraquinone Yellow. 3...... hannno-fi-ehloroanthraquinone Do. 4 l-am1no 6,7-diehloroanthraquinone Redldllishye ow 5....- Lamina-5,6,7,8-tetraehloroanthraqulnone...- Do. 6. Lamlno-Z-methylanthraquin0ne Do. 7--... 1-amino-2,4-dibromoanthraquinone Yellow. 8..." 1amino-4-methoxyanthraquinone Orange. 9.. l-arnino-4-methoxy-5-chloroanthraquinone Do. 10.-.. 1-am.ino-2-methyl--ehloroanthraquinone Redglsb ye ow. 11..-. l-amino-4-(4-ehlorobenzoyl)aminoanthraquinone. Orange.

11a--- 1'amino-5-(4 ch1orobenzoyl)aminoanthraquinone.-. Yellow. 11b-.. l,4-diamin0-2,B-dichloroanthraqulnone Orange.

EXAMPLE 12 N NH-CO \C (l l o 15 ii NH-CO l H0 o 4.76 g. of 1,4-diaminoanthraquinone and 11.9 g. of 2- hydroxy-S-phthalimido-l-benzoic acid are suspended in 250 ml. of nitrobenzene and heated to -110. To this suspension are then added dropwise within 2 hours, 5.22 g. of thionyl chloride, dissolved in 35 ml. of nitrobenzene. While stirring well, it is then heated for 3 hours to and then for a further 15 minutes to 185. After cooling to 80, the orange-red colored product is filtered off, washed with nitrobenzene, alcohol and acetone and dried. By this means are obtained 13.4 g. of a reddishyellow pigment of the above given formula having an excellent fastness to cross-lacquering, migration and light.

Pigments exhibiting similarly good fastness properties are obtained if, using otherwise the same procedure, the 11.9 g. of 2-hydroxy-5-phthalimido 1 benzoic acid is replaced by the equimolecular amount of 2-hydroxy-4- phthalimido-l-benzoic acid, Z-hydroxy 5 hexahydrophthalimido-l-benzoic acid, 2-hydroxy-5-(3 pyridinoylamido)-1-benzoic acid, 2-hydroxy-5-(2'-furanoylamido)- l-benzoic acid or 2-hydroxy-5-(1',8'-naphthalimido) 1- benzoic acid.

EXAMPLE 13 H0 NH-CO NH-CO-Q-Cl 8.92 g. of l-aminoanthraquinone and 12.82 g. of 2- hydroxy-S-(4'-chlorobenzoylamino) 1 benzoic acid are heated with 200 ml. of nitrobenzene to 90-95 At this temperature is slowly added dropwise, a solution of 5.23 g. of thionyl chloride in 20 ml. of nitrobenzene. After this addition has been made, the greenish-yellow suspension is heated within 30 minutes to 130-135 and then stirred for a further 3 hours at this temperature. After cooling to 90, the product is filtered ofl, washed with 7 nitrobenzene, alcohol and acetone and dried in vacuo at 8090. The yield is 14.6 g. The greenish-yellow pigment of the above given formula has a very good fastness to cross-lacquering and to light.

Pigments having similarly good fastness properties are obtained if the Z-hydroxy-S-(4'-chlorobenzoylamino)-1- benzoic acid, given in the example, is replaced by equimolecular amounts of a substituted 2-hydroxy-1-benzoic acid listed in Table H. The shades of color in the paper printing are given in column 3.

TABLE II Example Shade in paper number Hydroxybenzoie acid printing 14. Greenish yellow.

H0 01 H000 NHC oQ-m HO HOOC NH-O oQ-om 16 Yellow;

HO --NH-C O O C H! 17 Cl Greenish yellow.

18 NH-C QQ-Br 19-. on, Reddlsh yellow.

HO v 11000 -NH-O o--oon,

20....-'...... Ho A Do HO 0 oi --NH-C o-Q-NH-G 0-011;

no NH-O ONHC o-Q-m 22 I Greenish yellow.

HO Hooo -NH-C 0N02 24.- Yellow.

HO 7 H0 0 o NHC O-NH HOOC -NH 00- 9 EXAMPLE 26 nrp-oo-Q-ocm A solution of 4.1 g. of thionyl chloride in 25 ml. of nitrobenzene is added, while stirring well and within 1% hours, to a suspensionheated to 105-110--of 8.8 g. of 1-amino-6,7-dichloroanthraquinone and 9.9 g. of 2 hydroxy-S-(4'-methoxybenzoylamino)-1-benzoic acid. The orange-red suspension is stirred for a further 30 minutes at 105-110 and then heated for 3 hours to 130- 135. After cooling to 80, the reddish-yellow product is filtered off, washed with nitrobenzene, alcohol and acetone and dried.

12.9 g. of a reddish-yellow pigment of the above given formula are thus obtained, which has a very good fastness to cross-lacquering and light.

8.55 g. of 1-amino-4-benzoylaminoanthraquinone and 11.6 g. of Z-hydroxy-S-tetrachlorophthalimido-1-benzoic acid are heated with 200 ml. of nitrobenzene to 105- 110. Into the orange-red suspension are then added, within 1% hours, 3.41 g. of thionyl chloride dissolved in 25 ml. of nitrobenzene. After the evolution of hydrochloric acid has finished, the suspension is heated for 3 hours to 145-150. It is then cooled to 100 and the orange-red product of the above given formula is filtered off. It is washed with nitrobenzene and then with ethanol and dried.

By this means are obtained 15 g. of an orange-red pigment which has a very good fastness to cross-lacquering and to light.

EXAMPLE 28 O NH-C O NH-C O CH:

HaC-CO-NH Within 2 hours, 8.92 g. of thionyl chloride dissolved in 30 ml. of nitrobenzene are added dropwise to a suspensionheated to -95of 7.15 g. of 1,5-diaminoanthraquinone and 14 g. of 2-hydroxy-5-acetylamino-lbenzoic acid in 250 ml. of nitrobenzene. The suspension is maintained for 1 hour, while stirring well, at 100 and then heated for a further 3 hours to -145. After cooling to 100, the reddish-yellow product is filtered 01f, washed with nitrobenzene and alcohol and dried. By this means are obtained 16 g. of a reddish-yellow pigment of the above given formula, which has a very good fastness to cross-lacquering, migration and light.

If, in the above example, the 14 g. of 2-hydroxy-5- acetylamino-l-benzoic acid are replaced by 18.5 g. of 2- hydroxy-S-benzoylamino-l-benzoic acid, with otherwise the same procedure, then likewise is obtained a reddishyellow pigment having similar properties.

EXAMPLE 29 3.75 g. of 2' hydroxy-3',5'-diaminobenzoyl-l-aminoanthraquinone with 3.85 g. of p-chlorobenzoyl chloride in ml. of freshly distilled o-dichlorobenzene are refluxed for 7 hours. A yellow precipitate is formed which is filtered oil at 150. After the residue has been washed with o-dichlorobenzene, alcohol and acetone and then dried, 3 g. of a yellowish-brown pigment are obtained having a very good fastness to cross-lacquering.

The 2 hydroxy-3',5-diamiuobenzoyl-l-aminoanthraquinone is obtained by condensation of 2-hydroxy-3,5- diuitrobenzoic acid with l-aminoanthraquinone in nitrobenzene in the presence of thionyl chloride, and by subsequent reduction of the nitro groups by means of sodium dithionite in water-alcohol in the presence of soda.

If, in this example, the p-chlorobenzoyl chloride is replaced by equimolecular amounts of o-chloro, or o-methyl or p-methylbenzoyl chloride, with the procedure otherwise as described above, then likewise are obtained yellowish-brown pigments having good fastness to crosslacquering.

with salts, yields a reddish-yellow pigment having a good fastness to light, cross-lacquering and migration.

EXAMPLE 31 c1 0 NH-CO N 27.25 g. of 1,4 diamino-Z-chloroanthraquinone and 46.3 g. of 2-hydroxy-S-tetrachlorophthalimido-l-benzoic acid are heated with 500 g. of nitrobenzene to 105-110. Into the suspension are introduced, While stirring, 13.56 g. of thionyl chloride, dissolved in 50 m1. of nitrobenzene. The suspension is then heated for two hours to 140-145. The red suspension is filtered 011 hot, the residue washed with nitrobenzene and alcohol and dried. This produces 63 g. of a red pigment which has a very good fastness to cross-lacquering.

EXAMPLE 32 4.76 g. of 1,8-diaminoanthraquinone and 11.9 g. of 2- hydroxy-S-phthalimido-l-benzoic acid are suspended in 250 ml. of 1,2-dichlorobenzene and heated to 105-110. Into this suspension are added dropwise within one hour,

5.22 g. of thionyl chloride, dissolved in 20 ml. of nitrobenzene. While stirring well, the suspension is then heated for three hours to 150-156 and for a further minutes to 170-175 After cooling to 80, the reddish-yellow product is filtered off, washed with 1,2-dichlorobenzene, alcohol and acetone, and dried. By this means are produced 12 g. of a yellow pigment of the above given formula, which has an excellent fastness to cross-lacquering, migration and light.

EXAMPLE 33 40 g. of the pigment produced according to Example 27, 360 g. of hydrate of alumina, 600 g. of linseed oil varnish of medium viscosity and 2 g. of cobalt linoleate are mixed on a three-roller mill and ground. A printing ink is obtained which produces orange-red paper printings which have an excellent fastness to light.

EXAMPLE 34 To 100 g. of a stoving lacquer consisting of 58.5 g. of a 60% solution of a coconut alkyd resin in xylene, 23 g. of a 65% solution of a melamine gum-lac in butanol,

17 g. of xylene and 1.5 g. of butanol, is added 1 g. of the pigment produced according to Example 13 and 5 g. of titanium dioxide. The mixture is ground for 48 hours in a ball mill and the thus pigmented lacquer is sprayed on to a cleaned metal surface. After stoving at a yellow dyeing is obtained having a good fastness to light, crosslacquering and to weather.

EXAMPLE 35 67 g. of polyvinyl chloride powder (suspension polymerizate), 33 g. of dioctylphthalate, 2 g. of dibutyl tin dilaurate, 0.3 g. of stabilizer based on phosphate and 0.7 g. of the pigment, produced according to Example 1 by condensation of l-aminoanthraquinone and 2-hydroxy-5- tetrachlorophthalimide-l-benzoic acid, are mixed together and treated for 15 minutes on the mixing rollers which are heated to A sheet with a thickness of 0.4 mm. is subsequently produced on a calendering machine. It is dyed in a pure greenish-yellow shade, whereby the dyeing is resistant to heat and is'fast to migration.

What is claimed is:

1. A pigment of the formula wherein at most four Y-substituents represent chlorine, not more than two Y-substituents represent methyl, methoxy or bromine, and one of Y Y and Y represents H N- or benzoyl-NH, the remaining Y-substituents representing hydrogen, n represents 1 or 2, R represents alkyl of 1 to 4 carbon atoms, phenyl, p-diphenyl, naphthyl, phenyl substituted by one member selected from the group consisting of chlorine, bromine, methoxy and nitro, dichlorophenyl, pyridino or an NHR' group wherein R is alkyl of l to 4 carbon atoms, or phenyl, and the phenyl radical A is either further unsubstituted or substituted by halogen, methoxy or alkyl of l to 4 carbon atoms.

2. A pigment according to claim '1 wherein the substituents Y to Y represent hydrogen, chlorine, bromine, methyl or methoxy with the proviso that 3 to 7 of the Y substituents represent hydrogen and 0 to 2 of the Y substituents represent methyl, methoxy or bromine.

3. The pigment of claim 1 wherein all of Y to Y are hydrogens, phenyl radical A carries the methyl substituent ortho to the hydroxy group, the single radical 5. The pigment of claim 1 wherein all of Y to Y are hydrogens, the single radical 13 14 l is para to the hydroxy group, and R is the a-naphthyl References Cited group, and phenyl radical A is further unsubstituted.

6. The pigment of claim 1 wherein all of Y to Y are UNITED STATES PATENTS hydrogens, the Pfister 0 5 LORRAINE A. WEINBERGER, Primary Examiner 1 E. I. SKELLY, Assistant Examiner US. Cl. X.R.

is para to the hydroxy group and R is the 4-ch1orophenyl group, and phenyl radical A is further unsubstituted. 10 8-7, 40; 260-272, 347.3 

